CN109752434B - Electrochemical sensor for rapidly and selectively detecting quercetin and preparation method thereof - Google Patents
Electrochemical sensor for rapidly and selectively detecting quercetin and preparation method thereof Download PDFInfo
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- CN109752434B CN109752434B CN201910162484.2A CN201910162484A CN109752434B CN 109752434 B CN109752434 B CN 109752434B CN 201910162484 A CN201910162484 A CN 201910162484A CN 109752434 B CN109752434 B CN 109752434B
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Abstract
An electrochemical sensor for rapidly and selectively detecting quercetin and a preparation method thereof belong to the technical field of electrochemical sensors. Polymerizing PEDOT on a glassy carbon electrode by using an electrodeposition method, and then dropping 5. mu.L of WS onto the polymerized material2And (3) drying the aqueous dispersion, preparing an electrode compounded by tungsten disulfide and PEDOT, carrying out electrochemical detection on the quercetin in a solution taking Beriten-Robinson (Britton-Robinson) (0.2 mol/L) as a supporting electrolyte, wherein the composite electrode shows good electrocatalytic activity on the quercetin. The electrode can realize efficient, sensitive and selective detection of the quercetin, and can be successfully applied to determination of the content of the quercetin in the lotus leaves. The electrochemical sensor prepared by the invention has the advantages of easy preparation of electrode materials, low cost, simple and convenient operation, high speed and efficiency, high sensitivity and the like.
Description
Technical Field
The invention belongs to the field of electrochemical sensors, and relates to an electrochemical sensor for rapidly and selectively detecting quercetin and a preparation method thereof.
Background
Quercetin is an antioxidant, has double bonds between 2 and 3 positions in molecules, has 2 hydroxyls at 37 and 47 positions, and thus has the function of serving as a free radical acceptor generated in oxidation processes of metal chelation or grease and the like, and can remarkably inhibit the action of a cancer promoter, the growth of in-vitro malignant cells and the synthesis of DNA, RNA and protein of ehrlich ascites carcinoma cells in the aspect of cancer resistance. However, excess quercetin can induce inflammation, joint pain, and stiffness. Developed to date, various methods for measuring quercetin have been established, and among them, the methods widely used are mainly chromatography, such as thin layer chromatography, gas chromatography, liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry, and the like, and enzyme-linked immunoassay and electrochemical detection methods, which have respective advantages. At present, the quality control of the quercetin preparation standard in China is limited to chromatography. Generally, the detection of quercetin mainly utilizes chromatography, but the method is complex in operation and high in cost, and needs to be further improved.
The sensor can realize continuous, rapid, on-site and on-line in-vivo detection and analysis, and has the advantages of portability, feasibility, specificity, simplicity, sensitivity, high efficiency, low cost and the like, so that the sensor is widely applied to the related and similar fields of environmental monitoring and control, biopharmaceutical and clinical medicine, food safety and biological fermentation and the like. The electrochemical sensor can realize economical, practical, efficient, specific, sensitive, accurate, rapid and simple detection and analysis. Electrochemical detection of quercetin has been rarely studied. The cyclic voltammetry characteristics of quercetin on a glassy carbon electrode are researched in Jianbo Yu, Hui Jin, Rijun Gui, etc., the electrochemical oxidation mechanism of quercetin is discussed, and the oxidation products are analyzed and verified by liquid chromatography, wherein the linear range is 0.1-15 mu M. The method is finally applied to the determination of the content of quercetin.
Disclosure of Invention
The invention aims to provide a preparation method of an electrochemical sensor for rapidly and selectively detecting quercetin, which has the advantages of simplicity, practicability, high efficiency, sensitivity, accuracy, low price and the like.
The invention provides an electrochemical sensor for selectively detecting quercetin, which is a composite electrode of tungsten disulfide and poly (3, 4-ethylenedioxythiophene) (PEDOT).
The invention also provides a preparation method of the electrochemical sensor for selectively detecting quercetin, which comprises the following steps:
step 1: preparation of composite materials
Polymerizing PEDOT on the surface of a glassy carbon electrode, wherein a polymerization solution is an acetonitrile solution containing anhydrous lithium perchlorate and EDOT, and polymerizing for a period of time by using a constant potential method;
step 2: preparation of composite electrode
Taking 1mg/ml WS2And (3) dropwise coating the aqueous dispersion liquid on the surface of the polymerized glassy carbon electrode, and drying to obtain the tungsten disulfide and PEDOT composite electrode.
Further, in the step 1, the mass ratio of anhydrous lithium perchlorate to EDOT is 12-13: 1;
the volume ratio of acetonitrile to EDOT was 500: 1;
further, in the step 1, the polymerization time is 10-20s, and the voltage window is 0-1.35v。
Further, in said step 2, WS2The dosage is 3-10 μ L, and the drying temperature is 50-70 deg.C.
The invention also provides a using method of the electrochemical sensor for selectively detecting the quercetin, the prepared tungsten disulfide and PEDOT composite electrode is used as a working electrode, the platinum wire electrode is used as a counter electrode, the reference electrode is used as a saturated calomel electrode to form a three-electrode system, the Beriten-Robinson solution is used as an electrolyte solution, and the content of the quercetin in the solution to be detected is detected by using a differential pulse voltammetry method.
Preferably, the concentration of the birutan-robinson solution is 0.1mol/L to 0.2 mol/L.
The preparation method of the electrochemical sensor for rapidly and selectively detecting the quercetin has the advantages of low preparation cost, simple process and simple operation, the electrochemical sensor prepared by the method not only can successfully detect the quercetin, but also has the characteristics of high sensitivity (the lower detection limit can be as low as 0.07 mu mol/L), strong selectivity, good stability and the like, and the prepared composite electrode can be used for measuring the content of the quercetin in lotus leaves.
Drawings
FIG. 1 shows WS prepared in example 1 of the present invention2the/PEDOT composite electrode contains 10 μmCyclic voltammograms in berestan-Robinson (Britton-Robinson) solution of ol/L quercetin;
FIG. 2 shows WS prepared in example 1 of the present invention2Scanning Electron Microscope (SEM) images of the/PEDOT composite material;
FIG. 3 shows WS prepared in example 1 of the present invention2Differential pulse voltammogram of/PEDOT composite electrode in Bertany-Robinson (Britton-Robinson) solution containing different concentrations of quercetin;
FIG. 4 shows WS prepared in example 1 of the present invention2A linear plot of the different concentration responses of the/PEDOT composite electrode in Burriptan-Robinson (Britton-Robinson) solutions containing different concentrations of quercetin;
FIG. 5 shows WS prepared in example 1 of the present invention2Stability profile of the/PEDOT composite electrode;
FIG. 6 WS prepared for example 1 of the present invention with different pairs of substances2Detecting the interference condition of quercetin by a PEDOT composite electrode;
FIG. 7 is a high performance liquid chromatogram of a quercetin standard;
FIG. 8 is a high performance liquid chromatogram of an extract from lotus leaf.
Detailed Description
In order to make the technical problems, solutions and advantages of the present invention clearer, the following detailed description of a specific embodiment and the accompanying drawings are given, but the present invention is by no means limited to these examples. The following description is only a preferred embodiment of the present invention, and is only for the purpose of explaining the present invention, and should not be construed as limiting the scope of the present invention. It should be understood that any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Example 1
A preparation method of an electrochemical sensor for rapidly and selectively detecting quercetin comprises the following steps:
step 1: preparation of composite materials
Placing the glassy carbon electrode in 5 mL acetonitrile solution containing 0.0808 g of anhydrous lithium perchlorate and 5 mu L of EDOT for constant potential polymerization for 15 s, wherein the voltage window is 0-1.35 v;
step 2: preparation of composite electrode
5 μ L of 1mg/ml WS2The aqueous dispersion is applied dropwise to the surface of a glassy carbon electrode and then dried at 60 ℃ to give WS2a/PEDOT composite electrode.
For WS prepared as above2Electrochemical response of/PEDOT composite electrode to Quercetin in Bertanan-Robinson (Britton-Robinson) solution containing 10. mu. mol/L Quercetin 0.2mol/L and composite electrode to Quercetin at 0.38vAn irreversible oxidation peak is formed at the position, which shows that the composite electrode has good electrocatalytic oxidation activity to quercetin.
Electrochemical measurement of quercetin: quercetin of different concentrations was added to 0.2mol/L Bertany-Robinson (Britton-Robinson) solutions, and the peak current was linearly increased by measuring quercetin using differential pulse voltammetry using prepared composite electrodes, as shown in FIGS. 3 and 4,
the electrode has good linear relation (R) to quercetin2= 0.9860), wide linear range (0.1 [ mu ] mol/L-100 [ mu ] mol/L), high sensitivity and low detection limit (0.07 [ mu ] mol/L).
The performance of the electrochemical sensor for the detection of quercetin was evaluated, see fig. 5. As can be seen from FIG. 5, the prepared composite electrode has strong selectivity on quercetin, and has no obvious electrochemical response on rutin, luteolin, alkannin, chrysin and other substances. Even in the presence of various ions such as Cd2+、Pt2+、Pd2+、Cu2+In the complex environment existing at the same time, the electrochemical response of the quercetin is not obviously changed, so that the interference of some common ions is eliminated.
Evaluation of stability of electrochemical sensor for detecting Quercetin Using the above test method, Quercetin was continuously measured 20 times using prepared electrodes in Bertany-Robinson (Britton-Robinson) solution containing 10. mu. mol/L Quercetin 0.2mol/L, and the results are shown in FIG. 6. As can be seen from fig. 6, the electrochemical sensor prepared by the present invention has good stability.
Detecting and analyzing the actual sample of quercetin in lotus leaves: the purchased lotus leaves are cleaned, dried and crushed, are extracted by 70 percent ethanol in a backflow way for 1 h, are filtered, are taken out of filtrate for detection, and the result (figure 8) measured by high performance liquid chromatography is compared with the result (figure 7) of electrochemical detection, which shows that the constructed sensor is feasible for the detection and analysis of the quercetin sample in the lotus leaves.
Example 2
A preparation method of an electrochemical sensor for rapidly and selectively detecting quercetin comprises the following steps:
step 1: preparation of composite materials
Placing a glassy carbon electrode in an acetonitrile solution of anhydrous lithium perchlorate and EDOT for constant potential polymerization for 10 s, wherein the voltage window is 0-1.35 v; the mass ratio of anhydrous lithium perchlorate to EDOT is 12: 1; the volume ratio of acetonitrile to EDOT was 500: 1;
step 2: preparation of composite electrode
Taking 1mg/ml WS2Applying aqueous dispersion droplets onto the surface of a polymerized glassy carbon electrode, WS2The dosage of WS is 3 mu L, and WS is obtained after drying at 50 DEG C2a/PEDOT composite electrode.
Example 3
A preparation method of an electrochemical sensor for rapidly and selectively detecting quercetin comprises the following steps:
step 1: preparation of composite materials
Placing a glassy carbon electrode in an acetonitrile solution of anhydrous lithium perchlorate and EDOT for constant potential polymerization for 20s, wherein the voltage window is 0-1.35 v; the mass ratio of anhydrous lithium perchlorate to EDOT is 13: 1; the volume ratio of acetonitrile to EDOT was 500: 1;
step 2: preparation of composite electrode
Taking 1mg/ml WS2Applying aqueous dispersion droplets onto the surface of a polymerized glassy carbon electrode, WS2The dosage of WS is 10 mu L, and WS is obtained after drying at 70 DEG C2a/PEDOT composite electrode.
Example 4
A preparation method of an electrochemical sensor for rapidly and selectively detecting quercetin comprises the following steps:
step 1: preparation of composite materials
Placing a glassy carbon electrode in an acetonitrile solution of anhydrous lithium perchlorate and EDOT for constant potential polymerization for 15 s, wherein the voltage window is 0-1.35 v; the mass ratio of anhydrous lithium perchlorate to EDOT is 13: 1; the volume ratio of acetonitrile to EDOT was 500: 1;
step 2: preparation of composite electrode
Taking 1mg/ml WS2Applying aqueous dispersion droplets onto the surface of a polymerized glassy carbon electrode, WS2The dosage of WS is 7 mu L, and WS is obtained after drying at 60 DEG C2a/PEDOT composite electrode.
In conclusion, the preparation method of the electrochemical sensor for rapidly and selectively detecting the quercetin has the characteristics of high sensitivity (the lower detection limit can be as low as 0.07 mu mol/L), strong selectivity, good stability and the like, and the prepared composite electrode can be used for measuring the content of the quercetin in the lotus leaves.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. An electrochemical sensor for selectively detecting quercetin, which is characterized in that the sensor is a composite electrode of tungsten disulfide and poly (3, 4-ethylenedioxythiophene) (PEDOT);
the preparation method of the electrochemical sensor for selectively detecting the quercetin comprises the following steps:
step 1: preparation of composite materials
Polymerizing PEDOT on the surface of a glassy carbon electrode, wherein a polymerization solution is an acetonitrile solution containing anhydrous lithium perchlorate and EDOT, and polymerizing for a period of time by using a constant potential method; the mass ratio of anhydrous lithium perchlorate to EDOT is 12-13: 1; the volume ratio of acetonitrile to EDOT was 500: 1;
step 2: preparation of composite electrode
Taking 1mg/ml WS2The aqueous dispersion is dripped on the surface of the polymerized glassy carbon electrode and driedAnd obtaining the tungsten disulfide and PEDOT composite electrode.
2. The electrochemical sensor for selective detection of quercetin according to claim 1, wherein in step 1, the polymerization time is 10-20s and the voltage window is 0-1.35 v.
3. The electrochemical sensor of claim 1 for selective detection of quercetin, in step 2, WS2The dosage is 3-10 μ L, and the drying temperature is 50-70 deg.C.
4. The method as claimed in claim 1, wherein the prepared tungsten disulfide and PEDOT composite electrode is used as a working electrode, the platinum wire electrode is used as a counter electrode, the reference electrode is used as a saturated calomel electrode, a three-electrode system is formed, the biriten-robinson solution is used as an electrolyte solution, and the content of quercetin in the solution to be detected is detected by using a differential pulse voltammetry method.
5. The method of using an electrochemical sensor for the selective detection of quercetin according to claim 4 wherein the concentration of the Bertany-Robinson solution is 0.1-0.2 mol/L.
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| CN106996954A (en) * | 2017-06-14 | 2017-08-01 | 青岛科技大学 | A kind of photic electrochemical sensor and the method for determining sulfur-containing amino acid |
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| CN109369890A (en) * | 2018-08-29 | 2019-02-22 | 浙江工业大学 | A kind of poly- 3,4- ethene dioxythiophene Nanostructure Network film and the preparation method and application thereof |
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Patent Citations (5)
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|---|---|---|---|---|
| CN102288669A (en) * | 2011-05-04 | 2011-12-21 | 青岛大学 | Electrochemical method based on graphene-modified electrode for simultaneous determination of rutin and quercetin |
| CN104914149A (en) * | 2015-06-15 | 2015-09-16 | 天津工业大学 | Carbon fiber electrode used for diphenol microsensor |
| CN106996954A (en) * | 2017-06-14 | 2017-08-01 | 青岛科技大学 | A kind of photic electrochemical sensor and the method for determining sulfur-containing amino acid |
| CN108562633A (en) * | 2018-04-19 | 2018-09-21 | 山东农业大学 | A kind of optical electro-chemistry sensor and its detection method for detecting sulfadimethoxine |
| CN109369890A (en) * | 2018-08-29 | 2019-02-22 | 浙江工业大学 | A kind of poly- 3,4- ethene dioxythiophene Nanostructure Network film and the preparation method and application thereof |
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